Vinylidene chloride co-polymers



Patented June 6,1939 Q t .Q 7 s UNITED STATES PATENT OFFICE VINYLIDENE CHLORIDE CO-PO LYMEB B Edgar C. Brltton and Fred Lowell Taylor, 'Midland, Micln, assignors to The Dow Chemical Company, Midland, Mich, a corporation oi Michigan 1 v No Drawing. Application July 25, was.

Serial No. 221,107

'7 Claims. (01. 260- 80) This invention relates to the product obtained erties vary from fairly soft plastics to relatively by polymerizing together monomeric vinylidene hard masses as the proportion of the said ester chloride and the monomer' of at least one unsatdecreases. The co-polymers containing up to 'urated ester havingthe general formula 25 per cent of the unsaturated esters are ordi- 5 R x narily most readily prepared. In all cases the OH CH 0 g 6 softening point of the'co-polymers is substantially lower than that 01' polymeric vinylidene x chloride alone and in most cases the decomposiwhereln R is hydrogen, methyl, or halogen, one tioh temperature of the -P y s not mate- 10 X is halogen and the other X is hydrogen or the filthy lower than that Of po y e c v y d 10 same halogen. The esters defined by the above chloride- The -P y e y b w rked 'over formula are the allyl, Z-methylallyl, and 2-haloa Wider tu e a iie between the softenallyl esters of the haloand di-halo-acetic acids. ing p t and h d mp s n p int than an The invention relates particularly to the copolymeric vinyl d ne chloride.

polymers of vinylidene chloride and t mono. The herein-described co-polymers are some- 15 mers of allyl, methylallyl, or 2-chloroallyl-chlo- What soluble in (hexane at temperatures from roacetate. room temperature up to its boiling point but are we have found that 9, variety of useful ynsubstantially completely insoluble in the benzene thetic resinous and plastic products. may be prehydrocarbons a d in most of the common orgo pared by t copolymerization of vmyhdene garlic solvents including acetone, ether, the al-. 0 chloride and one or more of the unsaturated eshols, ethyl a t butyl e e y ters'of the halo-and di-halo-acetic acids having are Somewhat Soluble r are readily swelled by the general formula given above. Such products, ortho-dichlol'ohehzehei meho-ehlerebehzehe. 0! h i referred t as (go-polymers may be pretri-chlorobenzene at temperatures above 130 C.

pared by heating together a mixt of th Most of our herein-described co-polymers are 25 polymerizable compounds t temperatures from resistant to attack by concentrated sulphuric b t room temperature up t about 00 C acid and other strong mineral acids. Some of polymerization is facilitated by the use of catah -n e disco or sli htly after contact ly'sts capable of accelerating the reaction. Such with concentrated sulphuric acid but d not upcatalysts include, for example, light, benzoyl D to he decomposed thereby to any apprecla- 30 peroxide, mixtures of uranium nitrate or aceble extent- It may be S in a that the t t and benzoyl peroxide and t like. w co-polymers defined by the appended claims are uranium salts are employed in the mixture, the quite resistant to the a o of most common polymerizable compounds are ordinarily subjectacids and alkalies and or most 0! the common ed to the radiant energy from a mercury vapor garlic Solvents including the alcohols, ydro- 35 lamp or t direct stmlight. carbons, chlorinated hydrocarbons, ketones, etc., ou new go-polymeric products very in their at temperatures below 100 C., with the excepphysical properties depending upon both the 1510115 noted aboveidentity of the..compounds being co-polymerized The (IO-Polymer which we have found to nos- 40 and the proportion of vinylidene chloride and $9.55 the t desirable Properties 15 the 40 the said co-polymerizable compounds. We have Polymer of Vlhyhdene chloride and found t t t ee-po1ymers possessing the most allyl-chloroacetate. The chloroallyl-chloroaceutility are obtained when-the vinylidene chloride me, when mixed with menomeric vinylidene constitutes at least 50 per cent of the monomeric chloride and c'po lymerlzed therewlthdoes not mixture subjected to co-polymerization. When retard the holymenzatioh of the Vinyhdehe ehle- 4 5 t finished go-polymer contains over about 40 ride to the same extent as do similar proportions per cent of the unsaturated ester, the said 00- of most other ee-pelymerizeble co pounds. The

polymer is generally too soft and gelatin for harder co-polymers of vinylidene chloride and most purposes for plastic are employed 2-ChlOrOallyl-chloroacetate, i. 8., those containing These gelatinous products are, however useful less than about 25 per cent of the said ester, can 50 in the preparation of coating compositions and be cast strong films from Solutions of t e the like and are included in the scope of the d e -polymer i dloxahewhen the Said 0- present invention. when the co-polymer conp ly e is e it p du es ro er articles tains less than 40, and preferably less than about than do most of the tic-poly y de e 5| 25 per cent of the unsaturated esters, the propchloride under like conditions. The co-polymer of vinylidenelchloride and 2-chloroallyl-chloroacetate, even when unmodified by added plasticizers is capable of considerably more elongation without rupture than are most of the heretoi'ore known co-polymers of vinylidene chloride. It is also more elastic, especially when plasticized, than other similarly plast' zed vinylidene chloride co-polymers. For xample, a molded sample of a vinylidene chloride co-polymer containing about 12 per cent of 2-chloroallyl-chloroacetate, when stretched 10 per cent and released, wouldreturn at once substantially to its original size and shape. Most other vinylidene chloride co-polymers return to their original size only when stretched about 2 to 4 per cent. The unplasticized co-polymer of vinylidene chloride containing about 12 per cent of 2-chloro'allylchloroacetate is capable of about 100 per cent elongation after molding, while still relatively freshly prepared. Plasticized modifications of the same co-polymer exhibit elongations up to 250 per cent without rupture.

In the following table are set forth data showing the analysis of various of our new co-polymers produced from mixtures of monomeric vinylidene chloride and unsaturated esters defined by the general formula previously given. Co-polymerization was in each case carried out at C. In the table, the unsaturated ester is referred to as a modifier from its efiect in modifying the properties of the co-polymers as compared with those of polymeric vinylidene chloride. The proportion of reagents are given in per cent by weight and the amount of modifier entering into the copolymeric product is calculated fromthe chlorine analysis of the co-polymers obtained.

materials may be added in any expedient manner before or after co-polymerization, depending upon the effect such materials may have on the polymerization rate of the monomers or on the property of the finished co-polymcr.

Other modes of applying the principle of our invention may be employed instead of those explained, change being made as regards the materials or process employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed.

We therefore particularly point out and distinctly claim as our invention:

1. A co-polymer of vinylidene chloride and other polymerizable compounds at least one of which is an unsaturated ester having the general formula wherein R is a member of the class consisting of hydrogen, the methyl radical and halogen, one X is halogen and the other X is a member of the class consisting of hydrogen and the same halogen, at least 50 per cent of the weight of the copolymer being vinylidene chloride.

2. A co-polymer of vinylidene chloride and an unsaturated ester having the general formula hydrogen, the methyl radical and halogen, at

Table Percent Per- Percent Pply ncr- Extent of Percent Percent Percent vinyli- Run Modifier cent vinyliizatlon poly'mcrlchlorine chlorine modifier dene No, modidcnc tune, zation pcrin 00- in modiin 00- chloride fier chloride hours cent polymer tier polymer copolymer 1 2-chloroallyl-chloroacetate 15 85 65 62.0 70. 3 41. 97 10. l 89. 9 2.. do .4 20 80 93 56. 8 69. 44 41. 97 12.0 88.0 3 do 20 80 72 45. 9 69. 96 41. 97 10. 3 89. 7 4 ..-d0 20 80 71 52. 2 69. 92 41. 97 10. 5 89. 5 5 0,. 20 80 71 47. 7 69. 52 41. 97 11. 8 88. 2 6 Z-tGhtIBOl'OBIIYI dicbloroace- 20 80 42 39. l 71. 22 52. 36 9. 5 90. 5

a 7 do 20 80 47 48. 9 70. 71 62. 36 12. 0 88. 0 8 Allyl-chloroacetate 20 80 71 69. 3 70. 53 26. 36 5.7 94. 3 9 2-!tneihylal1yl chloroace- 20 80 71 50.8 69. 52 23. 87 7. 4 92. 6

pears at present to be that of vinylidene chloride and 2-chloroallyl-chloroacetate. The illustrative runs given in the table indicate that all of the compounds co-polymerized with vinylidene chloride quite readily but that the proportion of the unsaturated esters in the. finished co-polymer is considerably lower than the proportion of that ester in the monomeric mixture subjected to copolymerization. As has been stated previously our invention comprises the co-polymers of vinylidene chloride and the previously defined unsaturated esters, wherein at least 50 per cent of the co-polymer is vinylidenechloride. Our new copolymers may be modified in their physical properties and general appearance and utility by incorporating therein various effect materials such as coloring agents, fillers, and plasticizers. Such least 50 per cent of the weight of the co-polyme being vinylidene chloride.

3. A co-polymer of vinylidene chloride and an unsaturated ester having the general formula wherein R is a member of the class consisting of hydrogen, the methyl radical and halogen, at least 50 per cent of the weight of the co-polymer being vinylidene chloride.

4. A co-polymer of vinylidene chloride and 2- chloroallyl-chloroacetate wherein the amount of vinylidene chloride is at least 50 per cent of the weight of the co-polymer.

5. The process which comprises polymerizing a mixture of the monomers of vinylidene chloride and an unsaturated ester having the general formula wherein R is a member of the class consisting of hydrogen, the methyl radical and halogen, one x is halogen and the other X is a member of the class consisting of hydrogen and the same halogen, to produce a co-polymer at least 50 per cent of which is co-polymerized 'vinylidene chloride.

6. The process which comprises polymerizing a mixture of the monomers of vinylidene chloride and z-chloroallyl-chloroacetate to produce a. co-

polymer at least 50 per cent of which is copolymerized-vinylidene chloride.

7. A plastic composition comprising a co-polymer o1 vinylidene chloride and 2-chloroallylchloroacetate, the weight of vinylidene chloride being at least 50 per cent of the weight of said co-polymer.

. EDGAR C. BRITTON.

FRED LOWELL TAYLOR. 

